Polyester or polyacrylonitrile fibers dyed by quaternized or unquarternized azoanilino-toluene sulfonamidoalkyleneamine

ABSTRACT

Basic azo dyes are made by coupling an appropriate diazotized benzenoid or heterocyclic base with an N-dialkylaminoalkylene ( Alpha (N-alkylanilino))m- or p-toluenesulfonamide. Quarternization of the pendant dialkylamino group in the coupler may be carried out before or after coupling if desired to yield quaternary structures. The unquaternized structures, when properly dispersed, are applied to polyesters with excellent substantivity, outstanding fastness to sublimation and good fastness to light. The disperse unquaternized dyes are applied to polyacrylonitrile fabrics from a neutral or acidic bath; the water soluble quaternary structures are especially useful for coloring acrylic fibers.

United States Patent [191 Renfrew [451 May 6,1975

[ POLYESTER 0R POLYACRYLONITRILE FIBERS DYED BY QUATERNIZED ORUNQUARTERNIZED AZOANILINO-TOLUENE SULFONAMIDOALKYLENEAMINE [75]Inventor: Edgar E. Renfrew, Lock Haven, Pa.

[73] Assignee: American Aniline Products, Inc., Paterson, NJ.

[22] Filed: Nov. 3, 1972 [2]] Appl. No.: 303,429

[52] US. Cl 8/41 A; 8/41 C; 260/158;

260/205 [51] Int. Cl D06p 3/54; D06p 3/76 [58] Field of Search 8/41 A,41 C; 260/158 [56] References Cited FOREIGN PATENTS OR APPLICATIONS1,497,149 lO/l967 France 8/177 AB Primary ExaminerDonald Levy Attorney,Agent, or FirmArmstrong, Nikaido & Wegner [57] ABSTRACT Basic azo dyesare made by coupling an appropriate diazotized benzenoid or heterocyclicbase with an N- dialkylaminoalkylene [a(N-alkylanilino)]morptoluenesulfonamide. Quartemization of the pendant dialkylamino group inthe coupler may be carried out before or after coupling if desired toyield quaternary structures. The unquaternized structures, when properlydispersed, are applied to polyesters with excellent substantivity,outstanding fastness to sublimation and good fastness to light. Thedisperse unquatemized dyes are applied to polyacrylonitrile fabrics froma neutral or acidic bath; the water soluble quaternary structures areespecially useful for coloring acrylic fibers.

14 Claims, No Drawings POLYESTER OR POLYACRYLONITRILE FIBERS DYED BYQUATERNIZED OR UNQUARTERNIZED AZOANILINO-TOLUENESULFONAMIDOALKYLENEAMINE BACKGROUND OF THE INVENTION Since the advent offibers and textile material containing polyacrylonitrile, there has beenconsiderable research effort toward developing dyes of improvedproperties for such fibers. Polyacrylonitrile fibers are thosecontaining more than 85% polyacrylonitrile, including the well knowncommercially available fibers Orlon," Acrilan and Creslan." Modifiedacrylics are defined as containing 35 to 84% polyacrylonitrile andinclude the commercial fibers Dynel" and Verel."

It has been proposed to dye acrylic fibers with amine dyes either in theform of their salts in acid solution or their quaternary alkyl ammoniumderivatives made by treating a tertiary amino group with a quatemizingagent, such as dimethyl sulfate to form a water-soluble dye which can beapplied from aqueous solution. The quaternized dyes according to U.S.Pat. No. 3,480,612 have one or more of the following disadvantages:

1. They exhibit low affinity for acrylic fiber;

2. They produce dyeings of poor fastness to light;

3. They dye acrylic fiber in dull, unattractive shades,

4. They produce dyeings of poor levelness.

l have discovered certain new basic azo dyes which are not subject tothe foregoing disadvantages when quaternized and which in the form ofthe tertiary amine precursor can be applied to acrylic fibers from acidsolution or to aromatic polyester textile material by conventionalcarrier dyeing methods.

SUMMARY OF THE INVENTION In accordance with the invention there isprovided a dye of the formula:

l 4 B N N CH2 Q R s NH- (CH -Q In the above formula, B is a memberselected from the group consisting of Y R N R8 H l 0 8-0 and G X S 3wherein X, Y and Z are hydrogen, nitro, chlorine, bromine,

lower alkoxy, lower alkyl, cyano, sulfamyl, N- (lower alkyl)sulfamyl,N,N-(dilower alkyl)- sulfamyl, lower acylamido, trifluoromethyl, loweralkyl sulfonyl, carbamyl, N-(lower alkyl)carbamyl, and N,N'-(diloweralkyl)carbamyl;

R is hydrogen or methyl; and

R and R are hydrogen, lower alkyl, lower alkoxy, chlorine, bromine,nitro, sulfamyl, N,N-(dilower alkyI)-sulfamyl, cyano, and lower alkylsulfonyl;

R, is lower alkyl, cyano lower alkyl, and hydroxy lower alkyl;

R R and R. are hydrogen, lower alkyl, lower alkoxy, chlorine andbromine;

n is an integer having a value of 2-4,

0 is a member selected from the group consisting of R and R are methylor ethyl;

R is hydrogen, methyl, or ethyl; and

A 6 is a water soluble anion.

The dyes of the invention are applied to acrylic fibers and polyester ashereinafter described.

DETAILED DESCRIPTION The dyes are made in the conventional manner byadding a diazotized aminobenzene or diazotized amino heterocyclic baseto a solution of an appropriate coupling component.

Typical aminobenzenes useful as the diazotizable base in the couplingreaction are aniline, 0-, m-, or pphenetidine, 0-, m-, orp-aminobenzonitrile, sulfanilamide, metanilamide, N methylsulfanilamide,N,N'-dimethylsulfanilamide, N',N-dicyanoethylsulfanilamide, N,N-dimethylmetanilamide, paminoacetanilide, 2.4-dichloroaniline, 2,5-dichloroaniline, p-bromoaniline, 2,4-dimethoxyaniline,2,5-dimethoxyaniline, p-aminomethanesulfonanilide, mor p-nitroaniline, 4nitro-o-toluidine, 2-chloro-4- nitroaniline, 3chloro-4-nitroaniline,2,6dichloro-4- nitroaniline, 2-amino-5-nitrobenzonitrile, 2-methylsuIfonyI-4-nitroaniline, 4-nitro-o-anisidine, 4-nitro-o-phenetidine, 2,4-dinitroaniline, 6-chloro-2,4- dinitroaniline,6-bromo-2,4-dinitroaniline, and 2- amino-3,5-dinitrobenzonitrile. Amongthe foregoing substituted anilines, those bearing, in addition to othersubstituents, a single nitro group, para or meta to the amine function,are preferred because they provide enhanced light fastness in the finalproduct.

Typical amino heterocycles useful as the diazotizable base in thecoupling reaction are 2-amino-5- nitrothiazole,2-amino-4-methyl-5-nitrothiazole, 2- aminobenzothiazole,2-amino--ethoxybenzothiazole, 2-amino-6-methoxybenzothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-5-methylbenzothiazole,2-amino-4,fi-dichlorobenzothiazole, 2 amino-6-su|- famylbenzothiazole,2-amino-6-(N,N-dimethylsulfamyl)-benzothiazole, and 2-amino-5-bromobenzothiazole.

The aminobenzene intermediate is diazotized in the usual way by heatingit in an aqueous solution of strong mineral acid such as hydrochloricacid, cooling the resulting solution to a temperature of 0-l0C andadding thereto a quantity of sodium nitrite slightly in excess of thestoichiometric requirement. An alternate method of diazotizationinvolves dissolving sodium nitrite in concentrated sulfuric acid,heating to a temperature of about -70C, cooling the resulting solutionto 0-l0C and adding thereto the aminobenzene.

A diazonium salt solution of the amino heterocyclic base is prepared bydissolving sodium nitrite in concentrated sulfuric acid, heating to atemperature of about 60-70C, cooling the resulting solution to about Cand adding thereto first a mixture of acetic and propionic acid andthereafter the amino heterocyclic base. Alternatively, the aminoheterocyclic base can be mixed with concentrated phosphoric acid,stirred to solution at temperatures up to 65C, and cooled to below 0C.To the cold solution sodium nitrite and water are added dropwise withstirring.

Couplers useful in preparing the dyes are made by chlorosulfonation ofan N-alkyl-N-phenylbenzylamine followed by reaction with an N,N-dialkylalkylenediamine having from 2-4 carbon atoms in the alkylenechain. Amine bases which are suitable for the chlorosulfonation reactionare made by the reaction between an N-alkylaniline and a benzyl halide.Particularly useful sulfonyl chloride intermediates includea-tN-methylanilino)-m-toluenesulfonyl chloride,a-(N-ethyIanilino-m-toluenesulfonyl chloride, a-(N-cyanoethylanilino)-m-toluenesulfonyl chloride, a-(N-methyl-m-toluino)-m-toluenesulfonyl chloride, a-(N-ethyl-o-chloroanilino)-m-toluenesulfonyl chloride,a-(N-ethylanilino)-m-(6-chlorotoluenesulfonyl chloride,a-N-methylaniline)-m-(4-methoxytoluene)sulfonyl chloride,a-(N-butylanilino)-m-toluenesulfonyl chloride anda-(N-hydroxyethylanilino)-mtoluenesulfonyl chloride.

The sulfonyl chloride of the amine base is converted to the sulfonamideby treating it with a substantially stoichiometric quantity of theN,N-dilower alkylalkanediamine under conventional acid acceptingconditions. The reaction can be run in aqueous solution or in thepresence of excess diamine or in an inert organic solvent at atemperature of 60-l 00C. A small amount of an acid acceptor such assodium acetate may be useful to promote the reaction.

The structure of these and other useful couplers are thus:

l 4 N-CH R3 so v V---NH- (CH -Q wherein the substituents of the formulaare as defined aforesaid. The 4'-position is unsubstituted since it mustbe available as a coupling site to be useful. The position of thesulfamyl group has been assigned by analogy with the sulfonic acidstudies of Blanguy, L, H. E. Fierz- David, G. Stamm, Helv. Chim. Acta.25 N62 (I942) in which similar N-alkyl-N-arylbenzyl amines weresulfonated, yielding mainly the substituted m-toluenesulfonic acid,V=OH. However, other products were isolated and must represent otherpositions of the entering sulfo group. Thus, it is highly presumptivethat chlorosulfonation behaves similarly, and certain amounts ofsulfonamides of the structure are formed. They are useful couplers ifthe sulfonamide group is in the benzyl moiety.

The azo dyes of the invention are made by the reaction of the diazotizedbase with the coupler by adding the diazonium salt to a cold aqueoussolution of the coupler. A buffering agent, such as sodium acetate isadded to reduce the acidity to a pH of 5 to 7. The mixture is allowed toreact for 8-24 hours at room temperature and is thereafter filtered andwashed acid fee.

The desired azo product is thus obtained in the form of a wet cake.

The quaternary alkyl ammonium dyes of the invention are prepared byquatemizing azo dye obtained from the coupling reaction with analkylating agent, or by coupling the diazotized amine with the couplingcomponent as described above after the coupling component has beenquaternized. The novel dyes in their unquaternized form are converted tothe corresponding quaternary alkyl ammonium derivatives by treatmentwith conventional alkylating agents.

The quaternary ammonium derivatives of the coupling components and azodyes of the invention are prepared by known alkylation procedures, i.e.,by reaction of the amino group and an alkylating agent such as dimethylsulfate; a lower alkyl chloride, bromide or iodide, benzyl chloride;methyl p-toluene sulfonate and the like. The quaternization reaction isadvantageously done in an inert organic diluent such as,odichlorobenzene, in order to obtain a fluid reaction medium.

The anion A in the quaternary compound is an organic or inorganic watersoluble ion, including Cl, Br, 1, H H,PO,, ZnClf, CH SO', C,H,,S0{,C,,H,SO;,, l-lCOO', CH COO', C,,H,COO', and the oxalate, tartrate andcitrate ion.

The anion A may be introduced by the alkylating agent, eg., dimethylsulfate (providing methosulfate anion) or the anion may be introduced insalting out the quaternary compound from the quaternization reactionmass for example by addition of zinc chloride (providing thetrichlorozincate anion).

The quaternary dyes of the invention have excellent affinity for acrylicfiber (either alone or in blends with other textile fibers) and dye itin attractive level shades fast to light, washing and sublimation. Thenew quaternary dyes, being water soluble, are applied to acrylic fiberfrom aqueous solution preferably at the boil. Preferably the new dyesare applied from mildly acidic aqueous dyebaths of pH ca. 3 to 6. Thisis done either by setting the bath at the start with a suitable acidsuch as acetic, formic, tartaric, sulphuric or naphthalenesulphonicacid, alkali bisulphate or an acid alkali phosphate, or by adding anagent to the bath which produces acid during the dyeing process.Examples of such agents are the salts of volatile bases of strongnonvolatile acids, such as ammonium sulfate, and the water solubleesters of organic acids which saponify during dyeing, such as the methylor ethyl esters of aliphatic oxy acids, e.g., lactic, malic and tartaricacids. If the dyes are applied in mineral acid solution, the mineralacid also can be neutralized during dyeing by the gradual addition ofalkaline salts of weaker acids, e.g., sodium acetate. The dyes areapplicable with heating in open baths and in enclosed machines attemperatures above l00C. under pressure.

The unquaternized azo dyes of the invention are water-insoluble dyes forsynthetic hydrophobic fibers such as polyethylene terephthalate(Dacron), cellulose acetate and super-polyamide fiber for examplepolyhexamethylene adipamide (nylon 66). The unquaternized azo dyes,being water insoluble, are applied according to the well known dispersedyeing technique wherein the color is applied to the fiber from anaqueous dispersion of the dyestufi with the aid of a dispersing agente.g., sodium lignosulfonate. Disperse pastes and pow- 6 ders areprepared as described in US. Pat. No. The unquaternized azo dyes of theinvention also dye 3,685,952 of Edgar E. Renfrew. acrylic fibers from adisperse bath. When applied to polyacrylonitrile from an acid bath, theamine salt of To dyc ammauc polyester teimle 3 the acid is formed andthe polyacryonitrile is dyed in when added to water with or wnhom l' l 5bright shades having excellent fastness to light and wet forms a nearcolloidal aqueous dispersion from which processing the textile materialis dyed in the conventional manner My invention is further illustratedby the following at 40-l00C l04-2 l 2F) to give a colored fiberconexamples. taining about 0.0l-2 percent by weight dye (l00% colorbasis). '0 EXAMPLE I HC--l 1 a s u l ON-C c-n=n-@-n-ca 2 2 use A.Diazonium Solution In a suitable vessel equipped with a stirrer. aheater and thermometer were charged: 1S3 pans sulfuric acid (93-94%). Tothis were added l2.4 parts sodium nitrite below ISC. The mixture washeated to 'C. and then cooled to 0C. at which temperature I40 partsglacial acetic acid and 24 parts propionic acid was added below 3C.followed by 25.2 parts Z-amino-S-nitrothiazole.

The diazotiration mixture was stirred for 2% hours at 2 to +6'C.

B. Coupler Solution A mixture of parts N-( S-dieth lamino-n-propyl )-a-(N-ethylanilino l-mtoluenesul onamide in I000 parts water containing 48parts hydrochloric acid (320!) was stirred to solution at 65'C. It wasallowed to cool to 30C. at which temperature enough ice was added tolower the temperature to 2 C. Coupling D. Standardization To a ballmillwere charged 58 parts azo product from C 58 parts sodium sulfate. Thecharge was ballmilled l6 hours. E. Dyeing To a water bath at 50'C wasadded 0.3 cc of IO'Z sodium acetate 0.l cc of 56% acetic acid and 1 ccof dyeing assistant. To the hath was added the standardized dyestufl inan amount sufficient to provide a dyeing in the range of 0.5-2; onweight fiber. The total volume of the bath thus prepared was 250 cc.

Ill g. of Acrilun polyacrylnitrile skein was introduced to the bath andturned throughout dyein The temperature was raised slowly to 20 "F andafter 20 minutes lJ.l cc of 56% acetic acid was added.

The skein was added for 00 minutes on a boiling water bath and the potwas thereafter cooled to 70'C. The sltein was removed. rinsed inlukewarm water and dried. The dyed product had a violet shade of goodstrength and lightfastness.

EXAMPLE 2 4. Q L'I c" I CH N03 me n CH O8O o iil il 1. 1. Q

A. Diamtization I27 parts l0.3 parts I I6 parts parts 22 parts 8.Coupler 77 pans 500 parts C. Coupling ll2.S parts I750 parts D.Standardization parts 30 pans To a suitable vesicle was charged sulfuricacid (93-94; Below l5C sodium nitrite were added. The mixture was warmedto 65C and then cooled to 0C. At this temperature. a solution made upfrom galcial acetic acid propionic acid was added at 0 to 3C. and thiswas followed by the addition of Z-amino-S-nitrothiazole. Thediazotization mixture was stirred for 2% hours at 0 to 6C.

In a suitable vessel was dissolved by stirring at -65C.

{diethyl 3[a-( N-ethylanilino)-m-toluenesulfonarnidoln-propyl}methylammonium methyl sulfate (prepared by treating N-(3-diethylamino-n-propyl (N ethylanilino)-m-toluenesulfonamide withdimethylsulfate in chlorobenzene dispersed in water. The solution wascooled externally to 25C and then to 0C by adding ice.

The solution from part A was added to the solution of part B. Theaddition was made at 0 to 3C. Stirring was continued for twelve hoursduring which the temperature was allowed to rise to that of the room.

The azo product was collected on a filter and sucked dr The presscakewas then dissolved at BO QO C in water. and the solution was clarifiedthrough a filter coated with a diatomaceous earth filter aid. and washedthrough the filter with hot water. To the combined filtrates there wasadded at C sodium chloride. The mixture was stirred for [7 hours. Theazo product was collected on a filter and was washed with l0; sodiumchloride solution until the washings were no longer acidic. The azoproduct was dried. lt weighed 66.5 parts. containing 6.25 parts saltindicating a yield of 67.5%.

To a suitable mill was charged azo product from part C and anhydroussodium sulfate. The charge was milled l6 hours. The product dyedpolyacrilonitrile (Acrilan) from 0.2% and 0.4% solution in violet shadesof good strength and lightl'astness.

EXAMPLE 3 fz s so muca 3 N (CH3) 3 cn oso A. Diazonium Solution 20.7parts 45 parts 45 parts 120 parts 120 parts l0.5 parts 30 parts 8.Coupler 44l parts I056 parts In a suitable vessel equipped with astirrer. a heater and thermometer were charged: p-nitroanilinehydrochloric acid. 32%. and

water.

The mixture was stirred at C until solution resulted. The solution waspoured into a mixture of ice and water.

While maintaining the temperature at 0C by the addition of ice asneeded. there was added sodium nitrite in water.

The diazotization mixture was stirred for one hour at 0 to 5C. Excessnitrous acid was then destroyed by the addition of small portions ofsulfamic acid. The diazotiration solution was clarified by passinthrough a bed of diatomaceous earth on a ti ter. T e filter was washedwith a small portion of ice water and the washings collected with thefiltrate to make 750 parts by volume.

In a suitable flask fitted with stirrer. dropping funnel and drying tubewas placed chlorosulfonic acid. Then were addedN-ethyl-N-phenylbenzylamine below 25C. maintained Continued by externalcooling. The temperature was raised to 50C and held at this temperaturefor hours. The mixture was then cooled to C and added slowly to amixture of ice.

750 parts chlorohenzene and 250 parts water. adding enough ice to keepthe temperature below 2C. The chlorobenzene layer was allowed to settle.the aqueous phase was drained off. and the chlorobenzene washed severaltimes by decantation with ice water and then mixed with IOUO parts icewater.

To this was added with vigorous stirring at 2-4C. a solution of 76 partsN.N-dimethyll .B-propanediamine parts sodium carbonate 500 parts waterand 5 parts Tween 20" (a commercially available surface active material]adding ice as needed. The slurry was stirred l6 hours during whichperiod the temperature was allowed to rise to that of the room. Thechlorobenzene was drawn off. washed with two portions. each 300 partswater. and charged to a suitable flask which was fitted with a stirrer.thermometer and inversed DeanStarke trap. After removing residual waterby raising the temperature to |37"C.

89 parts dimethyl sulfate were added at 100C and the quaternization wascompleted by stirring for six hours at l(lt)C.

The quaternary product separated as a heavy oil. which was isolated bydecantation. It was washed with chlorobenzene at MP-95C. After steamdistillation of residual amounts of solvent. a clear aqueous solution ofthe quaternary salt was obtained which was diluted with water to 900parts by volume to make a 141% solution by volume. It

was analyzed by titration with diazotized p-nitro aniline and was foundto contain I27 parts trimethyammonium salt or 49% of theory.

280 parts of above 14% solution were mixed with 750 parts water. and

62 parts by volume sodium acetate solution (209i by volume) and cooledto 2C. (Coupling solution B] C. Coupling 385 parts by volume of ice colddiazonium salt solution A were added slowly at 2C to coupling solution Band stirred for one hour. To this parts sodium chloride were added andthe mixture stirred for 17 hours. during which time the temperature roseto 2tl25C. It was then heated to "C and I00 parts salt were added. Themixture was stirred for one hour at 80C The azo product was collected byfiltration on hard filterpaper and the presscake washed with sodiumchloride solution I066) and dried. Obtained was 47.3 parts azo product.containing 4.2 parts sodium chloride or 98% yield.

D. Dispersion 47.3 parts azo product C and 47.3 parts anhydrous sodiumsulfate were placed in to hallmill and milled for 24 hours. The productdyed polyacrilonitrile fabric ("Acrilan") from (1.4 and 0.8% solution inred orange shades of very good properties.

EXAMPLE 4 tic-"t1 o nq c a n @ii-ca SO2NH(CH2)3 mucu 2 6 A.Diazotilation 23 parts 2-amino-S-nitrothiazole were diazotized asdescribed in Example I.

B. Coupler t I4. I94 solution) C. Coupling l 25 parts I 000 parts 1 25parts D. Standardization 67.5 parts 67.5 parts A. Diazotization 34.5parts 80 parts 80 parts 5 parts 200 parts I parts 14.2 parts 40 parts 8.Coupler l05.6 parts 76 parts 97 parts C. Coupling 289 parts 750 parts700 parts 525 parts 2000 parts 300 parts Continued The diazoniumsolution A was added to 0C to coupler B. adding ice as necessary. Themixture was stirred for five hours allowing the temperature to rise to20-25C.

sodium chloride were added. the the azo product was collected on afilter after twelve hours stirring. The presscake was dissolved in waterat 85C. the solution clarified and the filter washed with hot water. Thewashings were combined with the filtrate and the azo productprecipitated by adding at 85C sodium chloride. The product was collectedby filtration at 40C. and the prcsscake washed free from inorganic acidswith IOZ salt solution. Obtained were 675 parts azo product. containinll.l parts sodium chloride. equivalent to 68' yield.

A ballmill was charged with azo d e C and anhy rous sodium sulfate andthe contents were milled for 24 hours.

It dyed "Acrilan from 0.5 and ll solutions in reddish blue shades ofgood strength and lightfastness.

EXAMPLE NH(CH 3 (CI-l 2 A suitable flask was charged with2-chloro-4-nitroaniline hydrochloric acid. 32%.

water and "Tween 20. and stirred for minutes at 80C. The mixture waspoured into a mixture of ice and water While maintaining the temperatureat 0C by the addition of ice. there was added sodium nitrite in water.

The diazotization mixture was stirred for one hour below 5C. Excessnitrous acid was then destroyed by the addition of small amounts ofsulfarnic acid. The diazotization solution was clarified by passing itthrough a bed of diatomaceous earth on a filter. the washings combinedwith the filtrate to make 700 parts by volume.

N( 3-dimethylamino'n-propyl )-a-( N-ethylanilino m-toluenesulfonamidewas prepared b treating N-ethyl-N-phenylbenzylamine with ch orosulfonicacid and further treating the sulfonyl chloride thus formed withN.N-dimethyll.3-propanediamine as described in Example 3. Chlorobenzenewas removed by steam distillation and the oily residue 184 parts) wasdissolved in enou h water containing hydrochloric acid 32 to make 600parts by volume.

(volume) coupler B were diluted with water and enough ice added to lowerthe temperature to 0C.

cold solution A were added simultaneously with sodium acetate solutionvol.) to keep the mixture slightly acid to Congo Red test papers.

The coupling mixture was stirred for l7 hours during which time thetemperature was allowed to rise to that of the surroundings.

sodium chloride were added and the temperature was raised to 68C. Theazo product was stirred for 48 hours. It was collected by filtration.and

the presscalte slurried in water sodium chloride were added at "C. themixture heated to 50C. the are product collected on a hard filter anddried.

Obtained were 137 parts of am product containing 7.2 parts sodiumchloride.

- Continued D. Ouaternization A suitable flask. fitted with stirrer.thermometer. and water trap with condenser. was charged with 68.5 partsazo product C and 390 parts chlorobenzene.

The mixture was heated to 137C to remove residual water and cooled toIOUC.

l8.3 parts dimethyl sulfate diluted with 3 L7 parts chlorobenzene wereadded during two hours and the stirring continued for 3% hours at thistemperature. The char e was poured at 84C into 500 parts water at 50Cand the lask rinsed with 385 parts hot water. and the rinse combinedwith chlorobenzene/water mixture. After l7 hours stirring. thechlorobenzene was drawn oft and washed several times with water. Theaqueous layer was combined with the washings and heated to 4UC.

262 parts sodium chloride were added. the charge was cooled to l2C. andthe quaternized dye was collected by filtration. The press-cake waswashed with ISZ sodium chloride solution and dried. Obtained was 68parts of product as a tacky mass. easily soluble in water.

E. Standardization 68 parts azo product were mixed with 68 parts sodiumsulfate.

It dyed Acrilan from 1 and 2; solutions in red shades of good strengthand lightfastness l3 EXAMPLE 6 Hc-t1 z s n l O N C C N N N CH A.Diazotization 3L8 parts B. Coupler 285 parts 715 parts l50 parts C.Coupling 1000 parts 38 parts D. Dis rsion 224 parts Sll parts I08 partsSO NH(CH 3 N(C H 2 Z-amino-S-nitrothiazole. equivalent to 0.22 mole.were diazotized as described in Example l.

by volume of an acidic solution of N( 3-diethylamino-n-propyl )-a-(N-ethylaminino l-m-toluenesulfonamide equivalent to 0.25 mole preparedin the manner as described in Example I.

water, and

salt were charged to a suitable vessel and cooled to UT.

A suitable mill was charged with azo product C Lignosol PTA" acommercially available ligninsulfilltllC acid material offered as adispersing agent) water.

The charge was milled for IE hours to make a l5;

aste. Eyed on "Acrilan from I and 2'1 solution in bright reddish blueshades and sgood strength and ii htl'astness (2t) hours+ 3 l. uhlimationS. wash astness 3 Dyed polyester from 2 and 4'24 solution in redvioletshades. Sublimation +5. +5. Light. 20 hrs.

15 16 EXAMPLES 7-62 The terms 0" and A correspond to the formula setforth in the Summary of Invention." In cases By following the proceduresof the preceding exam where no "A term is indicated eitherquaternization ples. the following dyes. providing dyeings of theindihas not been carried out or the pH used is not acidic cated hue. areproduced. 5 enough to ionize the l bra-p10 13 R R R R 11 Q A Hu 1 o n-O--cn (2')oc a n a a aren Yeliizgish a O-connO 0 x 2 n H a n(err orange 29 c 11 H a a 3 N(CH Bright orange Bright 10 11 00 50- c n n a a 3 N(CHorange 11 F a c n H H H 3 N(CH3)2 Yellowish 0 O Scarlet Br 12 C2H5 (3-)CH H H 3 N(CH3)2 Bluish o N Red Example B n R R R 11 Q A Hue 13 0 11(3'-)CH H n 3 N(Cll Scarlet 14 crr n 11 n a (011 c1 3113K? HZNOZS r;

15 050 mr-O crr n a n a mncu 01 Y 11 H i e owns:

3 2 3 3 2 orange 6 16 0 c n H H H 2 Nl1(Cll c1 Red C1 G e 17 O CH CH CNH H H 3 M611 cn oso omnge 9 7 2 6 R d 13 a ccrm-o C H (3 -)CH H H N(CllCl-I GS0 l l i 19 O C H rm-cu H u a Me H Red L... h. 2 5 3 I ii?! Iclaim:

I. A polyester textile material dyed with a compound of the form ula:

alkoxy. chlorine. bromine. nitro sulfamyl. N.N-(dilower alkyllsulfamyl.cyano and lower alkyl sulfonyl;

lower alkyl. cyano lower alkyl. and hydrox in which:

B is a member selected from the group consisting of wherein X. Y. and Zare R; is

lower alkyl; hydrogen. lower alkyl. lower alkoxy, chlorine and bromine:

R R4, and P are and 7 ii-1C1 n is an integer having a value of 2-4; 0 isa member selected from the group consisting of R R 5 o I e -N and II! AR and R. are methyl or ethyl; members selected from the group R ihydrogen. methyl. or ethyl; and CUflSlSflflg ol' hydrogenv nltro.chlorine, Aei a water soluble anion.

bromine. lower alkoxy. lower alkyl, cyano. sull'amyl. N-( loweralkyH-sulfamyl. N,N-(dilower alkyU-sulfamyl, lower 2. The polyester ofclaim I wherein said compound acrylamido. trilluoromethyl. lower alkyl40 is of the formula:

PIC-"- l g i N N @N-CH2@ S s sulfonyl. carhamyl. N-(lower alkylicarbamyland N.N-(dilower alkyl) 50 carbamyl'. hydrogen or methyl; and

0 NH(CH NH(C H 3. The polyester of claim 1 wherein said compound is ofthe formula:

. n (i l 0 N-C s N N N hydrogen or methyl; and members selected from thegroup consisting of hydrogen. lower alkyl. lower 4. The polyester ofclaim 1 wherein said compound is of the formula:

CH OSO SO NH (CH 3 N (CI-I 3 5. The polyester of claim 1 wherein saidcompound is of the formula:

SO NH (CH NH (Cl-l 6. The polyester of claim I wherein said compound isof the formula:

consisting of hydrogen. nitro. chlorine.

bromine. lower alkoxy, lower alkyl. cyuno.

N N-(dilower alkyll-sulfarnyl. lower ucylamido. trifluoromcthyl. loweralkyl sulfonyl. curhamyl. N-( lower r 0 N N N N-C 9 C1 c1 S02NH(CH2)3mucu 7. The polyester of claim 1 wherein said compound is of theformula: R, is

8. A polyacrylonitrile textile material dyed with a compound of theformula:

R, and R are in which:

B is a member selected from the group consisting of R is 3 N n N U and/C- O N 2 \g x 9 S wherem R,. R, and R4 are n is Q is X. Y. and Z an:members selected from the group 5 -N and ulkyllcurbamyl and N.N-(dilowerulkyl) curbamyl; hydrogen or methyl; and hydrogen or methyl; and

members selected from the group consisting of hydrogen. lower alkyl.lower Lllltox). chlorine. bromine. nitro. sulfumyl.

N.N-(dilower ulkyl lsulfamyl. cyuno. and lower alkyl sulfonyl; loweralkyl. cyuno lower alkyl. and hydroxy lower ulkyl;

hydrogen. lower ulkyl. lower alkoxy. chlorine and bromine;

an integer having a value of 2-4;

a member selected from the group consisting of -Cominued ll. Thepolyacrylonitrile of claim 8 wherein said R; and R, are methyl or ethyl;compound is Of the formula:

O N N N N-Cl'l CH 080 S NH o2 3 3 Ris hydrogen. melhyl or eihyl; and 12.The polyacrylonitrile of claim 8 wherein said compound is of theformula:

HCN c rr 5 H l l H o N-c S,c N N N-c 2 so NH(CH NH(CH e 2 2 3 3 2 C1 9.The polyacrylonitrile of claim 8 wherein said com- 25 13. Thepolyacrylonitrile of claim 8 wherein said pound is of the formula:compound is of the formula:

l ll ICZHS O N-C S C N N -cn H80 SO NH (CH )3NH (C H )2 OZN- VN N @N-CH2e 1 c1 02NH(CH2)3 NH(CH3)2 c 10. The polyacrylonitrile of claim 8wherein said 14. The polyacrylonitrile of claim 8 wherein said compoundis of the formula: compound is of the formula:

c n O N i-N=N N-C CH 6 s l CH 0S% so mca N(C H HC N

1. A POLYESTER TEXTILE MATERIAL DYED WITH A COMPOUND OF THE FORMULA: 2.The polyester of claim 1 wherein said compound is of the formula:
 3. Thepolyester of claim 1 wherein said compound is of the formula:
 4. Thepolyester of claim 1 wherein said compound is of the formula:
 5. Thepolyester of claim 1 wherein said compound is of the formula:
 6. Thepolyester of claim 1 wherein said compound is of the formula:
 7. Thepolyester of claim 1 wherein said compound is of the formula:
 8. Apolyacrylonitrile textile material dyed with a compound of the formula:9. The polyacrylonitrile of claim 8 wherein said compound is of theformula:
 10. The polyacrylonitrile of claim 8 wherein said compounD isof the formula:
 11. The polyacrylonitrile of claim 8 wherein saidcompound is of the formula:
 12. The polyacrylonitrile of claim 8 whereinsaid compound is of the formula:
 13. The polyacrylonitrile of claim 8wherein said compound is of the formula:
 14. The polyacrylonitrile ofclaim 8 wherein said compound is of the formula: